Production of alkinols



Patented Nov. 3,1942

, umrco STATES PATENT" OFFICE.

PRODUCTION OF -ALKINOLS Walter Reppe, Adolf Steinhoi'er, HermannSpaenig, and Karl Locker, Ludwigshafen-on- V the-Rhine, Germany,assignors, by-mesne assigmnents, to General Aniline & Film Corporation,New *York, N. Y., a corporation of Delaware No Drawing. ApplicationAugust 20, 1940, Serial No. 353,390. In Germany September 7, 1939Claims. (ci. 260-635) The present invention relates'to the productionacetylene in a cycle through a reaction vessel of alkinols (alcohols orthe acetylene series), 1. 6. wherein the copper acetylide is rigidlyarranged, alcohols containing a triple carbon linkage. preferably coatedto carriers. Together with or Numerous efforts have been made to preparein counter-current to the acetylene a solution of alkinols by condensingacetylene with aldehydes 5 formaldehyde is led through the vessel. Whenor ketones according to the formulae operating in this manner, it willbe found that RI RI after some time the copper acetylide loses itsHC=CH+ C0 C"C=CH crease the yield of alkinols.

R: R: 0H It is an object of the present invention to pro- R vide amethod of preparing alkinols from acety- HCzCIHz lene and aldehydes orketones, in particular from r J" acetylene and formaldehyde, whereby theactivity g of the copper acetylide catalyst and the good yield l ofalkinols are maintained for a long time. In W e 1 and R2 representhydrogen Orgamc order to obtain such result we have found that radicals.Until recently the condensation of t acetylene shouhi b brought intocontact aldehydes ketones with acetylene was only with the aldehyde orketone and copper acetylide Possible y starting from the Gl'ighal'dinthe presence of substances capable of preventpounds ofacetylene orfrom alkali metal com ing the formation of cuprene. pounds f a tyl ne ory working in the presence The substances employed in the execution oialkali metal, alkali metal alcoholates alkali the present inventionpreferably comprise one on metal amides. These condensations had to be aplurality of th elements gold, mercury, lead,

Carried t While Carefully excludihg Water antimony, bismuth, selenium,cerium, bromine or cause Otherwise the starting mammals would P iodineor their compounds. These elements may decomposed or converted intocompounds unsu1t-' be used in their elementary f rm rovided that ablefor the for a o alkinols- The p they do not react with acetylene byaltering the ation of alkinols y the above indicated Processesacetylenic linkage, as for example do free bromine has thereforepresented considerable diillculty or iodine h id l m t may also be usedand numerous p d ts h been p p s to So in form of their compoundsprovided that these overco thiscompounds do not add to the triplelinkage of Another method has ee P D to replace acetylene. Especiallygood results are obtained these Processes In this method the acetylidesby using compounds which contain more than one of the he vy metals ofthe first and second group of the above listed elements, e. g. theiodides of Of the Periodic til-b16816 U as y ts to bring mercury, leador bismuth. Among other suitable the direct condensation of acetyleneand aldeecompounds there may be mentioned mercury hydes ketsllesl In p rcopp scetylide oxide or phosphate, bismuth oxide or hydroxide, hasproved sulteble for example In the p bismuth oxynitrate',selenium-sulfur, selenium tion of alkhlols from acetylene and aldehydes,dioxide, the iodides of potassium, copper or silver. p ly m ld d Wh ning dis- 40 The substances preventing the formation oi n ou y, ppaoetylide or a copper cuprene may be dissolved or suspended in the re-DOllnd Capable of forming CODDBI acetylide is action liquid. They mayalso be applied to caradded to an aqueous solution of d yd riers'rigidlyarranged in the reaction vessel. prefand acetylene is led 111,preferably under D erably applied to the carrier together with theatmospheric pressure and admixed with an inert cgpper acetylidecatalyst,

diluent gas. In order to promote the-reactlon, Th following specificexamples are introduced the reaction mixt e s heated to y for thepurpose of illustrating preferred modes elevated temperatures, say tofrom 60 190 of executing the present invention. It is to be Whenacetylene is no longer absorbed. the understood that it is not ourintention to limit ture is allowed to cool, filtered off and thealkinols t same t reactants th employed or t th formed are separatedfrom'the filtrate by operating conditions described. The parts aretillation. When using the catalyst repeatedly, it by weight unlessotherwise t t will be found that its activity has decreased. Y E I 1 Inlarge scale operations, it is preferable to camp e carry out thereaction continuously by leading A mixture containing 50 parts of a 30per cent activity, and that side-reactions occur which deaqueousformaldehyde solution, 3 grams 6: copper and 0.25 part of calciumcarbonate are heated in a pressure-tight stirring vessel to 110' C. Amixture of acetylene and nitrogen (ratio by volume 8 :'1) is presedinuntil the pressure amounts to 20 atmospheres. Fresh acetylene is pressedin corresponding to the amount of acetylene absorbed. When acetylene isno longer absorbed the reaction mixture is filtered oif leavin: 18 partsof a brown-red mixture of (Ki per and cuprene. The filtrate is distilledin fractions. There are obtained unchanged formaldehyde and water andbutine-2-diol-L4 in a yield of 4 per cent calculated on the amount offormaldehyde used.

The reaction is repeated under otherwise identical conditions whileadding to the starting mixture 0.3 part of mercury oxide, or bismuthhydroxide, or potassium iodide or bismuth oxylodide or selenium-sulfur.when working up the reaction in the manner described above, no cupreneis found and the yield of butlne-z-diol- 1.4 amounts to from 18 to 20per cent when mercury oxide is used.

The copper and the substance preventing cuprene formation may be usedrepeatedly without cuprene being formed and the yieldbeing de- Thereaction is carried out in a pressure-tight tower made from stainlesssteel (900 centimeters length and 12 centimeters internal diameter)which has been charged with 70 liters of a catalyst prepared in thefollowing manner:

Cylindrical silicic acid gel particles of 4 millimeters diameter andmillimeters length are impregnated with a saturated aqueous solution ofcopper nitrate, dried and heated to 500 C. until nitrogen oxides are nolonger evolved. Silicic' acid particles are thus obtained containing acoating of 13 per cent of copper. I

Over this catalyst there are allowed to trickle at from 100' to 110 C.per hour 15 kilograms of a 30 per cent aqueous formaldehyde solution.Simultaneously, an excess of acetylene is led in the same direction in acycle under a pressure of '5 atmospheres. At the bottom of the tower anaqueous solution of butine-2-diol-l,4 isdrawn 01!. After some time theactivity of the catalyst is weakened so that the amount or formaldelnrdesolution introduced per hour has to be decreased. After 10 days thetower is plugged by the formation of cuprene.

The reaction is repeated under otherwise iden'- tical conditions whileusing a catalyst prepared in the following manner: '10 liters of silicicacid cylinders areimpregnated with a solution of 16 kilograms of coppernitrate and 3.2 kilograms of bismuth nitrate in dilute nitric acid.After drying and heating to 500 C., the cylinders are imnresnated with asolution of grams of'ammonium iodide in 2 per cent acetic acid and againdried at 300 (3.,

This catalyst remains effective for a long time so that after 15 weeksthe tower was still free from cuprene and the yield of butlne-2-diol-L4was still as high as at the beginning of the reaction. Although weprefer to prepare the copper acetylide catalyst within the reactionvessel from copper or copper compounds and acetylene. an alternativeprocedure is to impregnate carriers with copper acetylide in a separateprocess. for example by introducing acetylene into a, solution ofcuprous chloride or copper acetate in the presence of an agent capableof binding the acid and of a carrier substance;

Thev process is ordinarily carried out in aqueous medium a temperaturesfrom normal to 150 0., a tempera are of about from to 0. beingpreferred. Instead of or in addition to water an inert organic diluentmay be used. In case the formaldehyde solution used contains free acid,compounds capable of binding acids, such as calcium or magnesiumcarbonate, sodium bicarbonate, or magnesium oxide may be used. Thereaction should be carried out in weakly acid or neutral solution, whenstarting from aldehydes.

when using ketones, the reaction may also be weakly alkaline. Thehydrogen ion concentration, therefore, is advantageously kept betweenabout pH=2.5 and pH=12.

What we claim is:

1. In the process of producing alkinols by the interaction of acetyleneand a member of the group consisting of aldehydes and ketones in theliquid phase and in the presence of copper acetylide, the step whichcomprises performing the reaction in the presence of a compound ofbismuth.

2. In the process of producing alkinols by the interaction of acetyleneand aldehyde in the liquid phase and in the presence of copperacetylide, the step which comprises performing the reaction in thepresence of a compound of bismuth. i

3. In the process of producing alkinols by the interaction of acetyleneand an aldehyde in the liquid phase and in the presence of copperacetylide, the step which comprises performing the reaction in thepresence of a halogen compound .5. In the process of producing alkinolsby the interaction of acetylene'and formaldehyde in the liquid phase andin the presence of copper acetylide, the step which comprises performingthe reaction in the presence of a bismuth oxide.

WALTER REPPE. ADOLF S'I'EINHOE'ER. HERMANN SPAENIG. KARL LOCKER.

